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The reaction of cyclohexyl radicals with carbon tetrachloride
Author(s) -
Currie Jim,
Sidebottom Howard,
Tedder John
Publication year - 1974
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550060404
Subject(s) - chemistry , dichlorocarbene , cyclohexane , carbon tetrachloride , chlorine , reaction rate constant , radical , photochemistry , photodissociation , atmospheric temperature range , rate equation , thermodynamics , kinetics , organic chemistry , physics , quantum mechanics
The photolysis of azocyclohexane, carbon tetrachloride, and cyclohexane at 360 nm has been investigated over a wide temperature range. At moderate temperatures a chain reaction ensues from which the following approximate rate constants could be determined assuming 2CCl 3 . → C 2 Cl 6 , k 5 = 10 9.7 (303–673K):The really striking feature of the results is that they show that termination in bicyclohexyl [reaction (7)] is extremely slow:The root‐mean‐square rule for estimating the cross‐combination rateis also followed. The photolysis of carbon tetrachloride and cyclohexane at 250 nm has also been investigated. The reaction is complicated by the occurrence of two concurrent photolytic processes, the main one yielding trichloromethyl radicals and chlorine atoms, and the subsidiary one yielding dichlorocarbene and molecular chlorine. Nonetheless the results from this reaction can be interpreted in the medium temperature range 360–430K, where long chains are present, in terms of the rate constants derived from the azocyclohexane system.